CN103601236A - Preparation method of novel Au/Fe2O3-TiO2 nanotube catalyst - Google Patents
Preparation method of novel Au/Fe2O3-TiO2 nanotube catalyst Download PDFInfo
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- CN103601236A CN103601236A CN201310655646.9A CN201310655646A CN103601236A CN 103601236 A CN103601236 A CN 103601236A CN 201310655646 A CN201310655646 A CN 201310655646A CN 103601236 A CN103601236 A CN 103601236A
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Abstract
The invention relates to a preparation method of a titanium-iron composite supporter nanotube supported gold catalyst with high gold dispersity and controllable particle size. The TiO2 nanotubes synthesized by a hydrothermal process are used as a supporter and impregnated in a ferric hydroxide colloid, a sol perfusion process is utilized to prepare the titanium-iron composite supporter nanotubes, and lysine is used as a protective agent for noble metal nanoparticles and a linking agent between the noble metal particles and supporter, so that the small-size noble metal nanoparticles are uniformly supported onto the supporter in the formation process, thereby avoiding the step of previous functional treatment on the supporter, further synthesizing the supported noble metal catalyst material by one step, and greatly simplifying the synthesis steps. The composite supporter supported high-gold-dispersity catalyst can overcome the defects of low catalytic activity, small specific area, low dispersity of the active component gold, high accumulation tendency, high tendency to activity loss and the like, and has important practical application value. By reasonably selecting the composite supporter, regulating the structure and reasonably supporting the gold particles, the supported gold catalyst with smaller size and higher gold dispersity has higher catalytic activity.
Description
Technical field
The present invention relates to a kind of novel Fe
2o
3-TiO
2composite nano tube load type gold catalyst, the invention still further relates to concrete grammar and the feature of preparing this catalyzer.
Background technology
In recent years, the day by day serious survival and development that also directly threaten the mankind of atmospheric pollution.Load type gold catalyst, as a kind of eco-friendly new catalytic agent material, has shown wide application prospect in fields such as purifying air, environment protection.Large quantity research shows, the catalytic activity of gold is on carrier, just to have or improved due to high dispersing, the size of gold grain is one of key factor affecting catalyst activity, and in addition, the character of carrier and the preparation method of catalyzer also have material impact to the activity of catalyzer.Therefore selecting suitable carrier preparation method reasonable in design to impel golden high dispersing is the key that load type gold catalyst is realized high-efficiency catalytic activity.
Aspect the selection of carrier, TiO
2as a kind of high reactivity, non-toxic inexpensive, high, the eco-friendly novel environment friendly material of stability, be subject to extensive favor.TiO
2nanotube is as nano-TiO
2a kind of existence form, there is huge specific surface area and higher adsorptive power, can make the metal of load on it there is very high dispersity and stability, be one of current most active research object.In addition relatively single TiO,
2carrier, at TiO
2in add the second metal oxide to generate composite oxide carrier research caused that scientists pays close attention to greatly.This is because complex metal oxides has composite effect and the performance of single metal oxide carrier catalyzer as the catalyzer of carrier, thereby its catalytic activity is much higher than traditional single carried catalyst.Fe
2o
3as a kind of semiconductor material, there is narrower energy gap (Eg=2.2eV, λ=563nm), its absorption spectrum comparatively mates with solar spectral, can directly utilize sun power.Therefore by Fe
2o
3and TiO
2advantage combines, and uses Fe
2o
3modification TiO
2receive much concern.Based on above analysis, design a kind of novel titanium-iron complex metal oxides carrier with nano tube structure pattern, have the advantage of structural advantage and the complex metal oxides high catalytic activity of nanotube high-specific surface area concurrently, can overcome when defects such as the single carrier activity of procatalyst are low, carrier specific surface area is little.
At present, about the report of load type gold catalyst synthetic method, have a lot, as deposition-precipitation method, coprecipitation method, photochemical precipitation method and pickling process etc.Green non-poisonous amino acid, as one of essential material of human body, has abundant functional group, becomes study hotspot in recent years at aspects such as bionical synthetic and preparation nano materials.Amino based in amino acid and the interaction of Au, utilize amino acid as protective material, HAuCl
4the Au nanoparticle forming after being reduced by with amino acid molecular in amino effect, can effectively realize the high dispersing between gold particle.
Based on this, the present invention is first with the synthetic TiO of hydrothermal method
2nanotube is template, is impregnated in ferric hydroxide colloid solution, and adopting colloidal sol perfusion to prepare titanium-iron is complex metal oxides nano-tube support.And then adopt the auxiliary single stage method of Methionin to realize the high-efficient carrier of gold particle on complex carrier.By to the Effective Regulation of catalyst structure to realize the high-efficiency catalytic activity of catalyzer.
Summary of the invention
For realizing technical scheme provided by the present invention, be:
The synthetic titanate nanotube of the hydrothermal method of take is template, is impregnated in ferric hydroxide colloid, and stirring, ultrasonic, centrifugal, roasting, be composite nano tube carrier thereby obtain titanium-iron.Afterwards composite nano tube carrier is placed in to quantitative distilled water solution, the Methionin and the chlorauric acid solution that add successively different ratios, by the pH value of sodium hydrate regulator solution, ultrasonic afterwards, and in ultrasonic procedure, drip the borane reducing agent sodium hydride of respective amount, through centrifugal, repeatedly washing after, it is the nano tube supported type Au catalyst of complex metal oxides that products therefrom is titanium.
The hydrothermal synthesis method of wherein said titanate nanotube is: general～1.5g TiO
2powder (Detitanium-ore-type) is sealed in 70mL tetrafluoroethylene reactor with 10mol/LNaOH solution, be heated to～150 ℃ of reaction 12h of oil bath under agitation condition.Centrifugal, the floss of gained white is titanate nanotube.
Ferric hydroxide colloid preparation method is: by a certain amount of rare Fe (NO
3)
39H
2o solution is dropwise added drop-wise in the water of 100mL boiling, obtains henna Fe (OH)
3colloid.
Ultimate principle of the present invention is due to the synthetic TiO of hydrothermal method
2the formation mechanism of nanotube is curling mechanism, so TiO
2nanotube is the hollow tube of opening, and hole wall is laminate structure.When by TiO
2nanotube is impregnated in rare colloidal solution, and the tube wall of nanotube and interlayer are coated with one deck glue.Through roasting, colloid is decomposed into corresponding nanoparticle.Decompose the nanoparticle obtaining and form the uniform solid wall of one deck at nanotube tube wall, and and TiO
2nanotube interacts, and forming titanium-iron is composite nano tube carrier.Amino acid is owing to having (the NH of Liang Zhong functional group
2with-COOH); therefore there is stronger complex ability; can be simultaneously as the agent that links between the protective material of noble metal nano particles and noble metal and carrier; make small size noble metal nano particles when forming by uniform loading to carrier; avoided the carrier step of functionalization in advance; thereby can one-step synthesis loaded noble metal catalyst material, greatly simplified synthesis step.
Embodiment
For better understanding the present invention, below in conjunction with embodiment, the present invention is done further and described in detail, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment:
By 1.5g TiO
2powder (Detitanium-ore-type) is sealed in 70mL tetrafluoroethylene reactor with 10mol/L NaOH solution, be heated to～150 ℃ of reaction 12h of oil bath under agitation condition.Centrifugal, remove mother liquor, with after distilled water repetitive scrubbing, then use rare HNO
3solution stirs 12h after being adjusted to acidity (pH2-3), centrifugal, dries to obtain TiO
2nanotube.
Under high-speed stirring condition, take TiO prepared by 1.0g hydrothermal method
2nanotube is put in the ferric hydroxide sol of certain concentration, stirring at room 12h, and ultrasonic 3.5h, centrifugal afterwards, 80 ℃ of oven dry.After grinding in retort furnace roasting 2h at 400 ℃.It is complex carrier nanotube that gained pressed powder is the titanium-iron preparing.
Taking 2.0g titanium-iron is that complex carrier nanotube is in a beaker, add 15ml distilled water, in stirring, add successively isopyknic Methionin and chlorauric acid solution (concentration is all identical), stirring at room 0.5 hour, ultrasonic 0.5h, add afterwards excessive sodium borohydride solution, continue to be stirred to formation purple precipitation.Centrifugal, use distilled water repetitive scrubbing, dry, obtain Au/Fe
2o
3-TiO
2nano tube catalyst.
Claims (4)
1. a TiO
2nanotube, is characterized in that: it is the white floss that adopts hydrothermal method to prepare, and this floss need clean to neutrality repeatedly with distilled water, afterwards with dilute nitric acid solution be adjusted to acid after stirred for several hour, then be washed till neutrality with distilled water.
2. titanium-iron is a composite nano tube, it is characterized in that: by TiO claimed in claim 1
2nanotube is impregnated in the rare colloidal sol of ironic hydroxide, stirred for several hour, and ultrasonic a few hours, centrifugal afterwards, roasting, wherein said colloidal sol is extremely rare colloidal sol.
3. titanium-iron according to claim 2 is the preparation method of composite nano tube, it is characterized in that: described ultrasonic step is that low energy is ultrasonic.
4. a titanium-iron is composite nano tube load type gold catalyst, it is characterized in that: by titanium-iron claimed in claim 2, be that composite nano tube adds in the aqueous solution of Methionin and hydrochloro-auric acid, stir, after ultrasonic, the sodium borohydride that adds respective amount, wherein, described Methionin is identical with hydrochloro-auric acid volume, concentration is identical, and sodium borohydride is excessive.
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| CN201310655646.9A CN103601236A (en) | 2013-12-05 | 2013-12-05 | Preparation method of novel Au/Fe2O3-TiO2 nanotube catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105268434A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Crude terephthalic acid hydrofining catalyst |
| CN112091232A (en) * | 2020-09-11 | 2020-12-18 | 合肥工业大学 | Rapid preparation of Au-TiO under acidic condition2Method of composite construction |
| CN113617353A (en) * | 2021-08-02 | 2021-11-09 | 常州大学 | Preparation method of silicon carbide-based silver nano catalyst and application of silicon carbide-based silver nano catalyst in synthesis of ethylene oxide |
| CN113816879A (en) * | 2020-06-20 | 2021-12-21 | 万华化学集团股份有限公司 | Method for preparing calcium taurate and taurine through photocatalysis |
| CN114160162A (en) * | 2021-12-29 | 2022-03-11 | 天津工业大学 | Au/Co (OH)2Layered metal hydroxide hollow structure photocatalyst and preparation method thereof |
-
2013
- 2013-12-05 CN CN201310655646.9A patent/CN103601236A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105268434A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Crude terephthalic acid hydrofining catalyst |
| CN105268434B (en) * | 2014-07-24 | 2018-07-13 | 中国石油化工股份有限公司 | Hydrofining crude terephthalic acid catalyst |
| CN113816879A (en) * | 2020-06-20 | 2021-12-21 | 万华化学集团股份有限公司 | Method for preparing calcium taurate and taurine through photocatalysis |
| CN113816879B (en) * | 2020-06-20 | 2023-03-03 | 万华化学集团股份有限公司 | Method for preparing calcium taurate and taurine through photocatalysis |
| CN112091232A (en) * | 2020-09-11 | 2020-12-18 | 合肥工业大学 | Rapid preparation of Au-TiO under acidic condition2Method of composite construction |
| CN113617353A (en) * | 2021-08-02 | 2021-11-09 | 常州大学 | Preparation method of silicon carbide-based silver nano catalyst and application of silicon carbide-based silver nano catalyst in synthesis of ethylene oxide |
| CN113617353B (en) * | 2021-08-02 | 2023-09-22 | 常州大学 | Preparation method of silicon carbide-based silver nano catalyst and application of silicon carbide-based silver nano catalyst in ethylene oxide synthesis |
| CN114160162A (en) * | 2021-12-29 | 2022-03-11 | 天津工业大学 | Au/Co (OH)2Layered metal hydroxide hollow structure photocatalyst and preparation method thereof |
| CN114160162B (en) * | 2021-12-29 | 2024-01-05 | 天津工业大学 | Au/Co (OH) 2 Layered metal hydroxide hollow structure photocatalyst and preparation method thereof |
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Application publication date: 20140226 |